Treatment of cellulose textiles with a crease-proofing agent and with mixtures of nu-methylolstearamide and polyethylene



United States Patent 3,401,006 TREATMENT OF CELLULOSE TEXTILES WITH A CREASE-PROOFING AGENT AND WITH MIXTURES 0F N-METHYLOLSTEARAMIDE AND POLYETHYLENE Albert C. Perrino, Crauston, R.I., assignor to I.C.I./0rganics/Inc., a corporation of Rhode Island No Drawing. Filed July 8, 1963, Ser. No. 293,268 6 Claims. (Cl. 8115.6)

The present invention relates to the treatment of cellulosic fibers and fabrics with a synergistic composition containing polyethylene and an N-methylol monoamide of a higher carboxylic acid. The treatment improves the physical characteristics of fabrics such as handle, tear strength, wrinkle resistance and/or wrinkle recovery and abrasion resistance in such a way that the improvements are not destroyed by laundering or similar operations during normal use.

The treatment usually is carried out by impregnating the fabric or fibers with an aqueous dispersion of the treating agent and then heating the impregnated material for curing. It has been found to be particularly useful in conjunction with wash-wear cross-linking agents and/ or resins.

Treatment of cellulosic textiles with wash-wear cross linking agents and/or resins imparts a memory to the textile. That is, this treatment stabilizes the fibers in the configuration they had in the textile during the curing. Consequently, when a stress is applied to the treated textile and then released, the textile tends to return to the original configuration. This results in the textile exhibiting wrinkle-resistance and/or wrinkle recovery characteristics.

The cross-linking treatment, however, has an adverse effect on the tear strength, handle and abrasion resistance of the textile. Thus the cross-linked cellulosic textile, although exhibiting the beneficial characteristics of wrinkle-resistance and/0r wrinkle recovery behavior, has poor resistance to tear and abrasion during the use of the textile.

A number of softener-lubricating agents have been used in the textile industry to increase the tear strength, handle, abrasion resistance and wrinkle-recovery of crosslinked cellulosic textiles. These softeners are generally fatty acid derivatives such as fatty acid esters, amides and fatty amines and their quaternary ammonium derivatives, or polymers such as emulsified polyethylene, acrylics and silicones.

None of the softener-lubricating agents have been completely acceptable in all respects, however, For example, the initial beneficial effects on handle, tear strength and wrinkle recovery obtained with fatty esters, such as glyceryl monostearate, and quaternary ammonium compounds, such as distearyldimethylammonium chloride, are readily removed by washing and dry cleaning. The polymerics, such as polyethylene, exhibit some durability to washing, but the softening-lubrication effects are slowly removed by multiple washes, and the handle of the textile is poor.

The durability of the softening-lubrication effects of any agent is of the utmost importance. It is obvious that since the effects of the cross-linking are essentially durable to a number of washes and/0r dry cleaning, the effects of the softener-lubricant, as measured by tear strength, wrinkle recovery, abrasion resistance and handle, must also be durable to these treatments if these agents are to have any appreciable effect on the life of the textile.

It now have been discovered that treatment of cellulosic textiles with a composition containing polyethylene and an N-methylol monoamide of a higher carboxylic acid improves the physical characteristics of the fabrics such as handle, tear strength, wrinkle recovery and/or wrinkle resistance in such a way that the improvements are not destroyed by laundering, dry cleaning or similar operations during normal use.

The improvements in the physical properties of the textiles obtained with this mixture are not the average or mean effects to be expected by a simple combination of the two components, but are illustrative of a true synergism. This will become apparent on considering the examples. I

The polyethylene used is preferably of a type which is emulsifiable or in an emulsified form. Such types are readily available. For example, partially oxidized, low molecular weight (2,000) polyethylenes, which are readily emulsified, are available from Allied Chemical and Dye Corporation. A typical polyethylene, called A-C Polyethylene 629, has the following properties: melting point of 213-221 F.; penetration hardness (100 g., 5 sec., 77 F.) of 3-6 and an acid number of 14-17. Similar products are available from Eastman Chemical Products, Inc. under the names of Epolene E-lO, Epolene E-ll and Epolene E-12. These products have the following typical properties: ring and ball softening point (ASTM 0-36-26), 213-224 F.; penetration hardness (100 g., 5 sec. 77 F.), 1.5-2.5; acid number, 14-15; saponification number, 24-30; density (78 F.), 0.938- 0.950. Emulsions of these polyethylenes can be readily prepared using typical nonionic, anionic and cationic emulsifying agents, and are well known to those skilled in the art.

Polyethylene latices can also be employed. These are prepared by an emulsion polymerization process, that is, the latex particles are formed directly by polymerizing ethylene in water containing an emulsifier. Excellent results have been obtained with a polyethylene latex available from Spencer Industrials called Poly-Em No. 20017. Typical properties of the solid polymer are as follows: density (gm/cc), 0920-0935; average molecular weight, 15,000-30,000; melting point, greater than 200 F.

The amide is an N-methylol monoamide of a higher carboxylic acid such as linear or branched monocarboxylic acids containing 12 to 22 carbon atoms. The most satisfactory compound in this group is N-methylolstearamide.

The samples of stearamide employed in the examples which follow are generally commercial grades and therefore were mixtures of octadecanamide and hexadecanamide. These mixtures were completely acceptable for the purposes of this invention and should not be construed as limiting the scope of the invention.

The amount of N-methylol monoamide is about 25 to 80% by weight of the total of polyethylene and N-methylol monoamide.

The aqueous emulsions or dispersions containing polyethylene and the N-methylol monoamide can be made by mixing a dispersion of the polyethylene with a dispersion of the N-methylol monoamide, or by mixing the polyethylene and the N-methylol monoamide and dispersing the mixture in water with an emulsifying agent. For example, a nonionic dispersion of A-C Polyethylene 629 can be prepared by adding a mixture of 40 parts of A-C Polyethylene 629, 10 parts of a 10-m0le ethylene oxide adduct of nonyl phenol, and 3 parts of a 20% potassium hydroxide solution at 230 F. to 147 parts of water at 212 F. with rapid stirring, and allowing the dispersion to cool to 110 F. with moderate stirring. A dispersion of N-methylolstearamide can be prepared as described in Example I of US. Patent 2,944,921. These two dispersions can then be mixed in various amounts to give a mixture of polyethylene and N-methylolstearamide in any desired proportions. Those skilled in the art can readily envisage many modifications of this procedure.

It is necessary to cure the treated textiles to effect reaction of the N-methylol monoamide with the cellulosic textile. The exact nature of the cure depends on N-methylol monoamide being employed. For example, with mixtures of N-methylolstearamide and polyethylene, it has been found necessary to employ an acid or latent acid catalyst and elevated temperatures. By latent acid catalysts we mean substances which develop acidity during the curing stage. Particularly suitable materials include ammonium salts such as ammonium chloride, ammonium dihydrogen phosphate and ammonium thiocyanate, amine salts such as triethylamine hydrochloride, triethanolamine hydrochloride, and metal salts such as magnesium chloride, magnesium sulfate, zinc nitrate, aluminum sulfate, and the like. The amount of catalyst will depend on the amount of polyethylene and N-methylolstearamide to be deposited on the fabric. Satisfactory results were obtained with proportions of 2 /2 to 20%, preferably about of the weight of the mixtures of polyethylene and N-methylolstearamide. If an acid curable cross-linking agent and/or resin is applied simultaneously with the mixture of polyethylene and N-methylolstearamide, sufiicient acid or latent acid catalyst must be used to ensure a satisfactory cure of both compositions. Thus, if the amount of polyethylene and N-methylol monoamide deposited is 0.l2.5% of the dry weight of the textile and the amount of acid curable cross-linking agent and/ or resin is -15%, the amount of catalyst required is 0.05-15%.

The time and temperature required for the cure of the mixture of N-methylol monoamide and polyethylene are inversely proportional to one another, that is to say, the higher the temperature used, the shorter the period of time necessary. The temperature should generally be above 248 F. and preferably in the range of 284340 F. Excellent results have been obtained with 5-minute cures at 300 F. and 3-minute cures at 330 F.

Wash-Wear cross-linking agents and/ or resins with which said compositions can be used satisfactorily include acid curable (1) aminoplasts such as melamine-formaldehyde reaction products, guanamine and substituted guanamine reaction products, urea formaldehyde reaction products, formaldehyde reaction products of ethylene urea, 1,3-propylene urea, S-hydroxypropylene urea, triazones such as N-ethyltriazone and N-hydroxyethyltriazone, acetylene urea, 4,5-dihydroxyethylene urea, dimethylhydantoin, uron, formamide, ethyl carbamate and the like, their alkylated derivatives and the like, either singly or in combination with one another, (2) aldehydes such as formaldehyde, glyoxal, a-hydroxy adipaldehyde and the like, either singly or in combination with one another, (3) aldehyde derivatives such as tetramethylolacetone, diethyleneglycol acetal and the like, either singly or in combination with one another, (4) epoxides such as ethylene glycol diglycidyl ether, vinylcyclohexene dioxide and the like, either singly or in combination with one another, (5) ethyleneimine derivatives such as bisaziridinylcarbonyl, tris(1-aziridinyl) phosphine oxide and the like, either singly or in combination with one another; and alkaline curable agents such as (a) chlorohydrins such as 1,3-dichloropropanol-Z and the like, either singly or in combination with one another, (b) sulfone derivatives such as divinyl sulfone, divinyl sulfone B unte salt, fl, 9'-dihydroxyethyl sulfone and the like, either singly or in combination with one another, and sulfonium salts such as disodium tris (fl-sulphatoethyl) sulfonium inner salt. The amount of such agents and/or resins is that which would normally be used, for example, 1 to 20% of the dry Weight of the fabric.

This invention is not to be restricted to the aforementioned wash-wear cross-linking agents and/ or resins. The composition comprising N-methylol monoamide and polyethylene does not affect the wash-wear cross-linking agents and/or resins as such, but brings about modification of the properties of the textile itself. Consequently, it is an obvious advantage of this invention that the said composition can be used in conjunction with all types of wash-wear cross-linking agents and/or resins, the only restriction being that the said composition of N-methylol monoamide and polyethylene must be cured under conditions which efiect reaction of the N-methylol monoamide with the cellulosic textile as previously described. Consequently, if an acid curable mixture of polyethylene and N'methylol monoamide is used with an acid curable Wash-wear cross-linking agent and/or resin, both compositions may be cured simultaneously. If, however, an acid curable mixture of polyethylene and N-methylol monoamide, such as the mixture of polyethylene and N-methylolstearamide, is used with an alkaline curable wash-wear cross-linking agent and/or resin, such as disodium tris(5-sulphatoethyl)sulfonium inner salt, the said mixture of polyethylene and N-methylol monoamide must be cured at a separate stage. Example IV illustrates this technique.

The cellulosic textiles which may be used are textiles composed of cellulose or modified cellulose, such as cotton, rayon, linen, etc., and mixtures thereof, either with each other or with noncellulosics such as nylon, Perlon (polyhexamethylene adipamide or polycaproamide), Dacron (polyethylene terephthalate), Acrilan (an acrylic), etc. and the like. The textile may be in the form of filaments, fibers, threads, yarns, etc., or in woven, nonwoven, knit or otherwise-formed fabrics, sheets, cloths and the like.

The following examples illustrate the invention and the synergistic effect observed when using the combination of polyethylene and N-methylol monoamide. When the polyethylene employed is in the form of a latex, the designation (PL) is used. Otherwise, the designation (P) is used.

In these:

The wrinkle recovery evaluations were performed according to A.A.T.C.C. Tentative Test Method 664959.

Tear strength evaluations were run on the Elmendorf Tear Tester.

Abrasion resistance evaluations were performed by the flexing, folding bar (Stoll) method, Specifications CCC- T-191b, method 5300. Values given are averages of four sets.

Subjective evaluations were used for evaluating handle softness.

Durability to washing was determined by evaluating the textiles after multiple washes in a typical home laundry using a detergent such as Tide.

EXAMPLE 1 Effect of mixtures of N-methylolstearamide (MS) and polyethylene (P) on tear strength Mixtures of N-methylolstearamide and polyethylene vs. N-methylolstearamide.-A formulation was prepared containing N-methylolstearamide and polyethylene dispersed in an aqueous liquid containing:

Percent Dimethylol ethylene urea 5 9-mole ethylene oxide adduct of nonyl phenol 0.025 Acetic acid 0.05 Zinc nitrate hexahydrate 0.7

Paddings of mercerized 80 x 80 cotton fabric were prepared at wet pickup, air dried, cured at 310 F. for 4 minutes, and then given an after-wash with 0.1%

of a 7-mole ethylene oxide adduct of tridecyl alcohol and 0.1% soda ash. This was followed by wash cycles in a typical home laundry using Tide detergent. Tear strength tests were then performed with 'the following resu ts:

Ehnendori Tear Strength (Warp and Fill) Cone. of Softener in Bath (percent) Ratio M SIP Mixtures of N-methylolstearamide and polyethylene vs. polyethylene.The above procedure was repeated using a cure at 310 F. for 5 minutes. The fabrics were given wash cycles and tear strength tests were performed as above.

Elmendorf Tear Strength (Warp and Fill) Cone. of Softener in Bath (percent) Ratio MS/P EXAMPLE 2 Cotton fabrics were treated with the formulation of Example 1 and were then dry cleaned using Stoddard Solvent for 15 minutes. Tear strength tests gave the following results:

Cone. of Softener Elmendorf in Bath (percent) Ratio MS/P 'Iear Strength (Warp and Fill) EXAMPLE 3 Cotton fabrics (80 x 80 print cloth) were treated with the formulation given in Example 1. After the cure, the fabrics were dry cleaned for 15 minutes in Stoddard Solvent and then subjected to 10 wash cycles using Tide."

Elmendorf Tear Strength (Warp and Fill) Ratio MS/P or MS/PL Cone. of Softener in Bath (Percent) These examples clearly illustrate the utility of mixtures of N-methylolsteararnide and polyethylene. After dry cleaning and/ or multiple washings, the fabrics treated with said mixtures exhibit much superior tear strengths than fabrics not treated with these mixtures. Furthermore, it is apparent that the magnitude of this effect is not the average or mean of the values obtained with N-methylolstearamide or polyethylene, but is characteristic of a synergistic mixture. The following examples illustrate further.

EXAMPLE 4 A bath was prepared containing the following:

Percent Disodium tris (B-sulphatoethyl) sulfonium inner salt 12 Dimethylol hexahydropyrirnidinone-2 6.25 Zinc chloride 0.8 Softener-lubricant (as in the following table).

00110. 01f3 Sgrfltener in Ratio MS/P Tear Strength (lbs.)

HOJKDDD EXAMPLE 5 Mercerized x 80 cotton was preshrunk by washing in a home washer with a nonionic wetting agent prepared from nonyl phenol and 7 moles of ethylene oxide. The fabrics were dried and then padded through a formulation as given in Example 1 and cured at 310 F. for 5 minutes. Tear strength evaluations were performed after the fabrics were subjected to 10 Wash cycles.

Cone. of Softener Elmendorf Tear in Bath (percent) Strength (Warp and Fill) EXAMPLE 6 Fabric containing 65% Dacron (polyester) and 35% cotton was soaked in an aqueous suspension containing 2.5% dihydroxy dimethylol ethylene urea, 0.3% zinc nitrate hexahydrate and 0.1% of a 9-mo1e ethylene oxide adduct of nonyl phenol together with N-methylolstearamide and polyethylene. The fabric was cured at 300 F. for 5 minutes and subjected to 10 wash cycles using Tide.

Cone. of Softener Ratio MS/P Tear Strength in Bath (percent) (Fill Only) EXAMPLE 7 Effect of mixtures of N-methylolstearamide and polyethylene on abrasion resistance A cotton fabric was soaked to 70% wet pickup in an aqueous dispersion containing:

Percent Dimethylol ethylene urea 5 9-mole ethylene oxide adduct of nonyl phenol 0.025 Acetic acid a- 0.5 Zinc nitrate hexahydrate 0.1

and N-methylolstearamide and polyethylene in proportions and amounts shown in the table below. It was cured for 5 minutes at 310 F. Abrasion tests were made with the following results:

Ratio MS/P Stoll Abrasion (Cycles) Warp and Fill Cone. of Softener in Bath (percent) 7 EXAMPLE 8 Example 7 was repeated on mercerized cotton fabrics. The abrasion resistance of the fabrics was tested after 50 wash cycles using Tide, and the results were as follows:

Effect of mixtures of N-rnethylolstearamide and polyethylene on handle A formulation as described in Example 1 was used on 80 x 80 cotton print cloth. The cure was 310 F. for 5 minutes. After the mild soaping, the fabrics Were subjected to 50 Wash cycles using Tide detergent, and ironed before handle evaluation.

Fabric Cone. of Softener in Ratio MS/P Bath (percent) Handle (Softness) Fabric Rating g}- Excellent, Very Soft.

v II l Good.

I... Very Poor.

EXAMPLE Cotton fabrics were padded through the following formulation. The wet piokup was 70% Percent Dimethylol ethylene urea 4 Zinc nitrate hexahydrate 0.64

9-mole ethylene oxide adduct of nonyl phenol 0.025 Acetic acid 0.06 Softener (as in the following table).

After a 5-minute cure at 300 F., the fabrics were subjected to 10 wash cycles and ironed. Handle evaluations gave the following results:

Fabric Cone. of Softener in Ratio MS/P Bath Handle (softness) Fabric Rating II Good.

III Fair. (Noticea-bly inferior to II.)

I-...- Very Poor.

IV Excellent.

V- Noticeably inferior to IV.

I.. Very Poor.

8 EXAMPLE 11 Effect of mixtures of N-methylolstearamide and polyethylene on wrinkle recovery Cotton fabrics x 80 print cloth) were padded through a suspension containing 4% dimethylol ethylene urea, 0.7% zinc nitrate hexahydrate, 0.06% acetic acid, 0.025% of a 7-mole ethylene oxide adduct of tridecyl alcohol, and N-methylolstearamide and polyethylene in proportions and amounts shown in the table which follows. The fabrics were tested for tear strength and wrinkle recovery after 10 wash cycles with Tide. Both the tear strength and wrinkle recovery are given to illustrate that the higher tear strength of the fabric treated with the mixtures of N-methylolstearamide and polyethylene is not due to a concomitant lower wrinkle recovery, which is obviously undesirable, but that the superior tear strength of the fabric is accompanied by an increase in wrinkle recovery.

What is claimed is:

1. A method of treating a textile material containing cellulose textile which comprises applying to said textile a cellulose-reactive cross-linking crease-proofing agent and a mixture containing about 25-80% of N-monomethylol monoamide of a higher carboxylic acid containing about 12 to 22 carbon atoms and about 20-75% of fiber-lubricating emulsified polyethylene, and thereafter curing by heating the material to an elevated temperature.

2. A method of treating a textile material as set forth in claim 1 in which said monoamide is N-methylolstearamide.

3. A method of treating a textile material as set forth in claim 1 in which said curing is carried out in the presence of an acid catalyst.

4. A method of treating a textile material as set forth in claim 1 in which the curing is carried out at 300- 330 F. for 5 to 3 minutes.

5. A method of treating a textile material as set forth in claim 1 in which said cellulose-textile is cotton.

6. A method of treating a textile material as set forth in claim 1 including the step of drying the textile material before curing.

References Cited UNITED STATES PATENTS 1/ 1964 Goldstein et al 8-1156 4/1966 Shipee 1l7-l39.5

NORMAN G. TORCHIN, Primary Examiner.

H. WOLMAN, Assistant Examiner. 

1. A METHOD OF TREATING A TEXTILE MATERIAL CONTAINING CELLULOSE TEXTILE WHICH COMPRISES APPLYING TO SAID TEXTILE A CELLULOSE-REACTIVE CROSS-LINKING CREASE-PROFFING AGENT AND A MIXTURE CONTAINING ABOUT 25-80% OF N-MONOMETHYLOL MONOAMIDE OF A HIGHER CARBOXYLIC ACID CONTAINING ABOUT 12 TO 22 CARBON ATOMS AND ABOUT 20-75% OF FIBER-LUBRICATING EMULSIFIED POLYETHYLENE, AND THEREAFTER CURING BY HEATING THE MATERIAL TO AN ELEVATED TEMPERATURE. 